Substituted aryl sulphonic acids and processes of making the same



Patented J m-31,4939

UNITED STATES SUBSTITUTED ARYL SULPHONIC ACIDS AND PROCESSES OF MAKING THE SAME Arthur L. Osterhol, Newark, DeL, assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application June 17, 1938, Serial No. 214,886

12 Claims.

This invention relates to substituted aryl sulphonlc acids, and more particularly to conden- 'sation products of terpenes and aryl sulphonic acids and processes 01' making the same.

I have found that aromatic compounds substituted in the nucleus by a terpene radical and terpene phenol ethers, may be obtained by'condensingaromatic hydrocarbons or derivatives thbreoi with terpenes or with their oxygenated derivatives, using a suitable acid condensing agent. I have also found that such condensation products may be converted into sulphonic acid derivatives by treatment with the ordinary sulphonatl ng agents, or the process may also be carried out in a single stage by reacting a sulphonic acid derivative of an aromatic hydrocarbon with a terpene in the presence of a suitable acid condensing agent.

u The 'process according to the present invention is particularly applicable to aromatic compounds which are capable of sulphonation, for example, aromatic hydrocarbons of the benzene and naphthalene series and their homologues, and more particularly, non-halogenated aromatic hydrocarbons and their hydroxyl compounds, such as phenols; cresols, as p-cresol, m-cresol and o-cresol; naphthols, and the like.

The condensation may be carried out with fterpenes, e. g., pinene, turpentine, terpinene, terpinolene, dipentene, or with crude materials rich in such substances.

The products obtained in accordance with the 'present invention in the form of free acids or their alkali salts are clearly soluble in water and exhibit remarkable wetting, emulsifying and dispersing properties. They can be employed wherever a wetting, cleansing or emulsifying action-ls required, as, for example, in the treatmentof textile fibers, in the de-inking of paper 40 stockand in washing spray residues from fruit. They are particularly useful in acid solutions, for example, in the carbonizing bath or as spreading agents for dilute sulphuric acid used for weed control. They are also applicable in the preparation of dispersions of liquids or solidsinsoluble in water, for example, dispersions of petroleum oils, fatty oils, and waxes. Mixtures of suiphonlc acids, or their salts, with soaps, sulphonated oils, or other soap-like materials, may also be employed with advantage, for example, in dyebaths.

The invention will be described in greater detail in the following specific examples, which illustratetypical modifications, but the invention is not limited to these examples.

Example I 'To 272 parts by weight of alpha-pinene in a flask were added 188 parts by weight of phenol, the mixture warmed until solution occurred, then 4.5 parts by weight of p-toluenesulphonic acid added. The. flask was equipped with a reflux condenser and placed in an oil bath heated to C. The temperature of the mixture rose to C. The flask was removed from the oil bath, allowed to cool to 100 C., then again placed in the oil bath and heated to about 120 C. The temperatureoi the mixture rose rapidly, to about -170 0., even after the flask was removed from the oil bath and placed in cold water. The product, after cooling, was diluted with 250 parts by volume of benzene, washed thoroughly with 'water and dried by filtering through kieselguhr, and the solvent removed by distillation in vacuo at about C.

Then 115 parts by weight of the above product, dissolved inan equal weight of carbon tetrachloride was sulphonated by adding about 64 parts by weight of chlorosulphonic acid at 20-25 C. and maintaining the mixture at such temperature for hour, then pouring into 220 parts by weight 01' water containing 10% caustic soda.

Example II To 50 parts by weight of phenol were added 100 parts by weight of dipentene, 40 parts by weight of alcohol, the solutioncooled, and 10 parts by weight of a mixture of equal parts of concentrated sulphuric acid-glacial acetic acid were added, and the mixture heated for 5 hours on a steam bath, then washed repeatedly with salt water, a little ether added to prevent emulsification, the ether removed by placing the mixture on a steam bath, forming a dark condensate, which was distilled ofl up to ZOO-210 C., leaving a golden brown, almost odorless residue. Two parts by weight of this residue, dissolved in two parts by weight of carbon tetrachloride, were treated with 0.7 part by weight of chlorosulphonic acid, added drop by drop with stirring. The mixture heats and evolves hydrogen chloride. This product was neutralized by an excess of caustic soda. separating a clear amber layer containing the sodium 'salt of the dipentene-phenol sulphonate, which may be diluted with water to form a clear solution, which foams readily and forms extremely stable emulsions.

- Example III j To 50 parts by weight of phenol dissolved in 100 parts by weight of dipentene and 50 parts by ""To "asoiution oi 100 partsby weight of re- 7 sorcinol in 200 parts by'weight of pinene were p ture, the excess terpene was removed by steam the boiling point and refluxed for 4 hours. After cooling and washingwith water at room tempera- I mixture at such temperature for one-halt an hour. The product of this sulphonation may be obtained as the sodium sell; by neutralizin with 20% causticsoda solution, allowing to stand,

removing the water layer which separates, and,

recovering the sodium salt in paste iorm, which may be dried andpowdered, i1 desired.

Example IV added 1.5 parts by weight of p-toluene-sulphonic acid, the mixtureallowed to stand overnight, then I heated to 100 C. for 2 hours, then refluxed for 4' hours. 'After washing with warm water, the

' I excess terpene was removedby steam distillation,

the condensation product separated'irom the water layer, and dried. To 10 parts by weight of such condensation product,,dissolved in 10 parts by weight of carbon tetrachloride, were added '5 parts by weight oi! chlorosulphonic aoidat 20-25 C.,the mixture maintained at this temperature for about one-halt an hour, then neutralized with,

20% caustic soda solution to form the sodium 88.1001 thesulphonated condensation product.

Example V To a solution of '50 parts by weight of a commercial mixture oi. para-, metaand ortho-cresol in 100 parts by weight of turpentine was added 1 part by weight of p-toluene-sulphonic acid, the mixture allowed to stand overnight, then heated very slowly to 100' C. and maintained at such temperature for 1 hour, then the temperature gradually raised to the boiling point and refluxed for 4 hours. Ai'ter cooling, washing with water the excess terpene wasremoved by steam distillation, the condensation product separated from the water, and dried. To 61 parts by weight of the above condensation product, dissolved in an equal weight of carbon tetrachloride, were added 32 parts by weight of chlorosulphonic acid at 20-25 C., the mixture maintained at such temperature for one-halt an hour, then neutralized with 20% caustic soda solution to form the sodium salt of the sulphonation product.

Example VI To a solution of 50 parts by weight of commercial xylenol in 100 parts by weight of dipentene was added 1 part by weight of p-toluenesulphonic acid, the mixture allowed to stand overnight, then heated to 100 C. for 2 hours, then to its boiling point and refluxed for 4 hours, cooled, washed with water, and steam distilled to remove the excess terpene, the water separated, and the condensation product dried. Oi! such dry condensation product, 129 parts by weight were dissolved in an equal weight of carbon tetrachloride and sulphonated by adding 64 parts by weight of chlorosulphonic acid at 20- 25 C. and maintained such temperature for onehali an hour, then neutralizing by addition of v of carbon tetrachloride.

auaseo 7 weight oi alcohol, were added 10 parts by weight or concentrated hydrochloric acid, the mixture heated slowly to C. and maintained at that temperature for 4 hours. then heated'slowly to Example VII To a solution of parts'by weight of mph-- thalene in 200 parts by weight oi'dipentene were added, 10 parts by weight of p-toluene sulphonic acid. The mixture was slowly heated to the boilv ing point and refluxed for eight hours. After "cooling I and washing with warm water, the

excess terpene was removed by steam distillation, I the product was separated from the water, and

was dried. 'Oi the'dry condensation product, 2

parts by weight, dissolved in an equal weight of I trichlorethylene, were sulphonated by 1 part by maintaining that temperature for one hour. The

sulphonation product was neutralized by the addition of 20% caustic soda solution.

Example VIII the mixture allowed to stand 'overnight under then'heated under carbon dioxide, at 100 C. for

one: hou'n the temperature raised to 130 (Lior two hours and finally heated two hours atv C. The resulting mixture was then waterwashed and steam distilled whereby water-soluble portions and volatile oils were removed, leavv ing a 217 parts by weight of a condensation prodnot of pinene and .o-cresoliot a light yellow color.

One hundred parts by weight of'thls condensa-,

tion product was dissolved in 300 parts by weight 1 weight of chlorosulphonic acid at 35-40", C. and

part by weight clip-toluene sulphonic acid and 5 I a blanket of'carbon-dioxide. This mixturevwas I This solution was cooled to 20 C. Fifty-two parts by weight 01 chlorosulphonic acid was then slowly added to this solution with cooling and stirring such that the temperature stayed at 20-25 C. This treatment required about thirty minutes. The mixture was then stirred for an additional three minutes, neutralized by the addition of 231 parts by weight of a 10% solution of sodium hydroxide and rendered slightly alkaline by the addition of 3 parts by weight oi. sodium carbonate, to form the sodium salt of the sulphonation product of the pinene-o-cresol condensation product. This product was recovered as tan, friable material in a yield of 147 parts by weight by distilling water and solvent out of the reaction mixture until the residue was a paste and then drying this paste in a vacuum oven at 60-65 C.

Example IX The condensation product of pinene and mcresol was produced by following the condensation procedure described in Example VIII, with the substitution of 150 parts by weight of m-cresol for the o-cresol. As a result of this procedure 303 parts by weight of a pale yellow product was obtained. This produce was then sulphonated by treatment with chlorosulphonic acid following the sulphonation procedure described in Example VIII, except in that 220 parts by weight or a 10% aqueous sodium hydroxide solution and 6 parts by weight of sodium carbonate were used. As a result of this procedure 157 parts by weight 0! the sodium salt of the sulphonation product of the condensation product of pinene and nin color.

messes Example X The condensation product of pinene and pcresol was produced by following the condense,- tion procedure described in Example VH1, with the substitution of 150 parts by weight of p-creso] for the o-cresol. As e. result of this procedure 267 parts by weight of a. pale yellow condensation product was obtained. This product was. then suiphoneted with chlorosulphonic acid following the sulphonetion procedure of Example VIII, except in that 5 parts by weight of sodium carbonate was used. As a result of' this procedure 150 parts by weight of the sodium salt of the sulphonation product of the oondensetlon product of pinene and p-cresol was obtained. This product was greyish white in color.

Example XI The condensation product of terplncne and phenol was produced by following the condense.- tion procedure described in Example rm, with the substitution of 200 parts by weight of terpinene and 150 parts by weight of phenol for the piuene and o-cresol, respectively. As a. result of this procedure 126 parts by weight of e. waterwhlte coudensetion product of terpinene and oh 12103 were produced. This product was then sulohonsted by the sulphonetion procedure of Example ll, except in that 242 parts by weight of a. aqueous sodium hydroxide solution and 1 port by weight of sodium cerbonete were used. 3.3 a. result of this procedure, 139 parts by weight of the sodium salt or" the sulohonstion product of terpinene-phenol condensate were obtained. This product was ten in color.

The shove products. obtained in accordance with this invention, in the form of the free sulphonetlon product or the alkali salt thereof, are clearly soluble in water and form remarkably efiective wetting, emulsifying end dispersing agents. They may be employed wherever a. wetting, cleansing or emulsifying action is desired, e. g., in the treatment of textile fibers end the like. They are particularly useful in acid solutiers, e, in acid dye baths, in the emulsificetion or netroleum oils, fetty oils, and the llke.

This application is e continuetion=in-pert of my application, Serial No. 142,486, filed 13, 1937.

What I claim and desire to protect by Letters Patent'is:

1. The process of preparing sulphonic acids of high cleansing. wetting and emulsifying power, which consists in condensing an unpolymerized terpene-with a. member of the group consisting of non-halogenated members of the benzene and naphthalene series and their hydroxy compounds, and svlphoneting the product.

2. The condensation product obtained by the process of claim 1.

3. The process of preparing sulphonic'acids of high cleansing, wetting and emulsifying power,

which consists in condensing pinene with phenol I and sulphonating the product- 4. The condensation product obtained by the process oi claim 3.

5. ihe process of preparing sulphonic acids of high cleansing, wetting and emulsifying power, which consists in condensing dipentene with phenol and sulphonating the product.

6. The condensation product obtained by the process of claim 5.

7. The process of preparing sulphonic acids of high cleansing, wetting and emulsifying power, which consists in condensing turpentine with phenol and sulphonating the product,

8. The condensation product obtained by the process of claim '7.

9. The process of preparingsulphonio acids of high cleansing, wetting and emulsifying power, which consists in condensing an unpolymerlzed terpene with a. eresol and sulphoneting the product.

10. The condensation product obtained by the process of claim 9.

11. The processor preparing sulphonic acids of high cleansing,wetting end emulsifying power which consists in condensing an unpolymerized. terpene with m-cresol and sulphonating the product.

12. The condensation product obtained by the process of claim 11.

' L. OSTERHOF. 

